Department of Chemistry, Clemson University, 219 Hunter Laboratories, Clemson, SC 29634-0973, USA.
Department of Chemistry & Chemistry Research Center, Laboratories for Advanced Materials, US Air Force Academy, 2355 Fairchild Dr, Suite 2N255, Colorado Springs, CO 80840, USA.
Chempluschem. 2021 Apr;86(4):549-557. doi: 10.1002/cplu.202100042.
A series of cocrystals of Ph P=E (E=O, S, Se) with organoiodines were studied to understand the roles of noncovalent interactions including chalcogen (ChB) and halogen (XB) bonding in their formation. The structure of the cocrystal of Ph P=S and 1,2-diiodotetrafluorobezene was determined, which demonstrates a similar chalcogen⋅⋅⋅iodine XB pattern to the previously reported isomorphic Ph P=Se structure. The cocrystalline structures resulting from the combination of 1,3-diiodotetrafluorobenzene (1,3-F DIB), as well as iodopentafluorobenzene, with all three triphenylphosphine chalcogenides, were also determined. The (Ph P=Se) ⋅ (1,3-F DIB) cocrystal presents a rare example of a selenium⋅⋅⋅organoiodine ChB. The observed ChB and XB interactions have normalized distance parameters (R ) ranging from 0.80 to 0.98. The strength of the XB and ChB interactions were analyzed using natural bond orbital (NBO) theory, with calculated energies falling between 3.14 kcal/mol and 12.81 kcal/mol.
我们研究了一系列 Ph P=E（E=O、S、Se）与有机碘的同晶型物，以了解非共价相互作用（包括硫属元素（ChB）和卤素（XB）键）在它们形成过程中的作用。确定了 Ph P=S 和 1,2-二碘四氟苯的同晶型物的结构，其展示了与先前报道的同构 Ph P=Se 结构相似的硫属元素···碘 XB 模式。还确定了由 1,3-二碘四氟苯（1,3-F DIB）以及碘五氟苯与所有三种三苯基膦硫属元素组合而成的同晶型结构。（Ph P=Se）···（1,3-F DIB）同晶型物呈现了一个罕见的硒···有机碘 ChB 的例子。观察到的 ChB 和 XB 相互作用具有归一化距离参数（R）在 0.80 到 0.98 之间。使用自然键轨道（NBO）理论分析了 XB 和 ChB 相互作用的强度，计算出的能量介于 3.14 kcal/mol 和 12.81 kcal/mol 之间。
